Leiden Institute of Chemistry, Einsteinweg 55, 2300 RA Leiden, The Netherlands.
J Am Chem Soc. 2011 Oct 26;133(42):16754-7. doi: 10.1021/ja206689t. Epub 2011 Oct 5.
Several techniques rely on electron-nuclear interactions to boost the polarization of nuclear spins in the solid phase. Averaging out of anisotropic interactions as a result of molecular tumbling strongly reduces the applicability of such hyperpolarization approaches in liquids. Here we show for the first time that anisotropic electron-nuclear interactions in solution can survive sufficiently long to generate nuclear spin polarization by the solid-state photo-CIDNP mechanism. A 10,000-fold NMR signal increase in solution was observed for a giant biomolecular complex of a photosynthetic membrane protein with a tumbling correlation time in the submicrosecond regime, corresponding to a molecular weight close to 1 MDa.
几种技术依赖于电子-核相互作用来提高固相中核自旋的极化度。由于分子翻滚导致各向异性相互作用的平均化,大大降低了这些超极化方法在液体中的适用性。在这里,我们首次表明,溶液中的各向异性电子-核相互作用可以持续足够长的时间,通过固态光 CIDNP 机制产生核自旋极化。在亚微秒范围内翻滚相关时间的光合膜蛋白与一个巨型生物大分子复合物的溶液中,观察到了 10000 倍的 NMR 信号增强,这对应于接近 1 MDa 的分子量。